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J. Phys. Chem.

B 1999, 103, 6539-6546 6539

Isosteric Heat of Adsorption: Theory and Experiment

S. Sircar,* R. Mohr, C. Ristic,† and M. B. Rao


Air Products and Chemicals, Inc., 7201 Hamilton BouleVard, Allentown, PennsylVania 18195-1501

ReceiVed: February 2, 1999; In Final Form: May 24, 1999

The isosteric heats of adsorption of the components of a gas mixture are critical variables for design of
adsorbers for gas separation. They can be unambiguously defined by the Gibbsian Surface Excess (GSE)
model of multicomponent adsorption. These variables can be experimentally measured by multicomponent
differential calorimetry (MDC) and directly used to describe nonisothermal behavior of practical adsorbers.
There is no need to make simplified assumptions about the nature and size of the adsorbed phase, as required
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by conventional adsorption thermodynamic models, to define the isosteric heats. Pure gas isosteric heats of
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adsorption of N2 and CO2 on a pelletized silicalite sample were measured using a MDC and a data analysis
algorithm based on the GSE model. The silicalite sample behaved like a homogeneous adsorbent for weakly
polar N2 adsorption. The presence of polar alumina binder in the silicalite sample introduced significant
heterogeneity for more polar CO2 adsorption.

Introduction a unit amount of the adsorbent.7-9 The bulk gas phase is defined
by its pressure (P), temperature (T), and the mole fraction (yi)
The isosteric heats of adsorption of the components of a gas of component i. The Gibbsian adsorbed phase is defined by an
mixture are key thermodynamic variables for design of practical arbitrarily chosen Gibbs’ interface where the local adsorbate
gas separation processes such as pressure swing and thermal density and compositions are the same as those of the
swing adsorption.1,2 They determine the extents of adsorbent homogeneous bulk gas phase. The extent of adsorption of the
temperature changes within the adsorber during the adsorption ith component of the gas mixture is given by its Gibbsian surface
(exothermic) and desorption (endothermic) steps of the pro-
excess (nm i , mol/g) which can be experimentally measured.
cesses. The adsorbent temperature is a key variable in determin-
They are independent of the location of the Gibbs’ interface as
ing the local adsorption equilibria and kinetics on the adsorbent,
long as it is within the bulk gas phase. Thus, the GSE model
which ultimately govern the separation performance of the
does not require that the exact size, structure, location, composi-
processes.
tion, and the density of the actual adsorbed phase be known.
Although many different types of differential and integral
The pressure and temperature of the Gibbsian adsorbed phase
heats of adsorption have been defined in the adsorption
are the same as those of the bulk gas phase.
literature,3-6,8,9 the differential isosteric heats of adsorption are
found to be most useful for practical design of adsorbers.8,9 They All conventional experimental methods for gas adsorption
can be (a) unambiguously defined using the Gibbsian Surface studies (volumetric, gravimetric, chromatographic, etc.) measure
Excess (GSE) model of multicomponent adsorption system, (b) nmi as functions of P, T, and yi under equilibrium conditions
directly measured calorimetrically or indirectly estimated from (multicomponent equilibria) and nm i as functions of time under
multicomponent adsorption equilibrium data, and (c) conve- transient conditions (multicomponent kinetics). They represent
niently used to describe heat balance using the transient GSE the true experimental variables.8
model of batch or flow adsorbers.8-10 Figure 1b schematically shows the conventional model used
The purpose of this work is to (a) review the thermodynamic for multicomponent gas adsorption equilibrium. In this case,
definitions of multicomponent isosteric heats of adsorption and the interface between the bulk gas phase and the adsorbed phase
their use in process design under the framework of the GSE is located exactly where the local density and composition of
model,7-9 (b) discuss limitations of the conventional definition the adsorbed phase approach those of the bulk gas phase. The
of isosteric heats of adsorption using actual amounts adsorbed adsorbed phase is defined by its actual volume (Va, cm3/g) and
as variables, and (c) demonstrate the use of the GSE model in the extent of adsorption of component i is given by its actual
estimating isosteric heats of adsorption from the data obtained amount adsorbed (nai , mol/g).
by a differential adsorption calorimeter. The total void volumes (bulk gas phase + pores in the
adsorbent) for both systems of parts a and b of Figure 1 are the
Isosteric Heats of Adsorption by GSE Model same (V0, cm3/g). They can be experimentally measured by
helium expansion. The actual adsorbed phase volume of Figure
Figure 1a schematically shows the GSE model for an
1b, on the other hand, cannot be unambiguously estimated
equilibrium multicomponent gas adsorption system containing
without making extraordinary assumptions about its structure,
particularly for the meso-micro porous adsorbents of practical
* Corresponding author.
† Present Address: Chemical Engineering Department, Pennsylvania State interest. Another key point to note is that Va is an unknown
University, College Park, PA. function of nai and T (or P, T, and yi).
10.1021/jp9903817 CCC: $18.00 © 1999 American Chemical Society
Published on Web 07/20/1999
6540 J. Phys. Chem. B, Vol. 103, No. 31, 1999 Sirca et al.

Figure 1. Schematic drawings of various adsorption models: (a) Gibbsian surface excess model; (b) conventional model; (c) model for constant
P, T experiment using a pure gas.

A comparative mass balance for the components of the gas It can be shown from the thermodynamic analysis of the GSE
mixture using the models of parts a and b of Figure 1 yields8 model8,9 that, for an ideal gas mixture, one has

i ) (ni - V Fyi) ) V (F xi - Fyi )


nm
[ ] [ ]
a a a a a a
(1) δU° δQ
- )+ ) qdi ) +(qi - RT) (3)
δnm
i m
T,nj*i δnm
i m
T,nj*i
where F and Fa are, respectively, the molar densities of the bulk

[ ]
gas phase and the actual adsorbed phase (Figure 1b), and δln(Pyi)
xai ()nai /∑nai ) is the mole fraction of component i in the actual qi ) RT2 (4)
δT nm
adsorbed phase (Figure 1b). i

Equation 1 clearly shows that nm i ≈ ni only when (F xi .


a a a

Fyi) for a multicomponent gas and when Fa . F for a pure gas. where U° (cal/g) is the total internal energy of the adsorption
Otherwise, there can be a large difference between experimen- system of Figure 1a. The quantity dQ (cal/g) represents the
differential amount of heat to be removed (or added) to the
tally measured nm a
i and calculated ni values. Furthermore, ni
m
a system for a differential change (dnm i ) in the surface excess of
and ni may be approximately equal to each other for the more m
component i at constant T and (nj*i ). The quantity qdi (cal/mol)
selectively adsorbed component of a gas mixture (xai . yi), but
in eq 2 is called the differential heat of adsorption. Equation 3
the difference between nm a
i and ni can be large for the less
gives the relationship between qi and qdi for an ideal gas
selectively adsorbed components of the same gas mixture even
mixture.
though (Fa . F).8
Equation 4 shows that qi can be estimated by knowing the
The conventional approach to develop adsorption thermody-
differential change in the partial pressure (pi ) Pyi) of
namics is to assume nm i ≈ ni and then follow the model of
a
3,4 component i of a gas mixture due to a differential change in
Figure 1b. This can lead to ambiguous and erratic thermo-
system temperature at constant values of nm i . This can be easily
dynamic and kinetic interpretation of experimental adsorption
data. The problem can be resolved by developing adsorption achieved for a pure gas by measuring adsorption isotherms (nm i
thermodynamics and kinetics based on the GSE model of Figure as functions of P) at different constant temperatures8,9 but the
1a.8,9 use of eq 4 for gas mixtures containing two or more components
The equilibrium GSE model defines the isosteric heat of can be formidable if not an impossible task.8 It will be shown
adsorption of component i (qi, cal/mol) as the negative of the later that direct calorimetric estimation of qi for multicomponent
differential change in total enthalpy (H°, cal/g) of the closed systems is much easier.
system of Figure 1a for a differential change in the surface Equation 3 shows that qdi and qi can be easily interchanged
excess of component i (nm as the design variable of choice. We prefer to use qi because of
i ) at constant system temperature (T)
and constant values of surface excesses of other components its traditional thermodynamic connotation with reference to eq
m 4 and its conventional counterpart (eq 21). The second reason
(nj*i ) of the system8,9
to choose qi is its temperature independence over a large range

[ ]
δH° of temperature.9
- ) +qi (2) The GSE model of transient mass and heat balances for ad-
δnm
i m
T,nj*i (de)sorption of an N-component ideal gas mixture in a packed
Isosteric Heat of Adsorption: Theory and Experiment J. Phys. Chem. B, Vol. 103, No. 31, 1999 6541

adsorbent column yields:9,10 adsorbed and equilibrium gas phases are µa and µ, respectively.
For an ideal gas,11
mass balance of component i

( ) [ ]
µa ) µ ) µ*(T) + RT ln P (11)
δnji δ(Gyi)
)- i ) 1, 2, ....N (5) dµ*
δt z δz t µ* - T ) h* (12)
dT
ni ) Fbnm
i + Fyi (6)
where µ* and h* are, respectively, the chemical potential (molar
heat balance Gibbs free energy) and the molar enthalpy of the pure gas at

CAFb () {
δT
δt z
)-
δ
δz
[GCg(T - T0)] } + Fb∑qi ( ) δnm
i
δt z
+
temperature T and a pressure of 1 atm. They are functions of T
only. The molar gas volume for an ideal gas is ν ) (RT/P) and

( )
t
that for the adsorbed phase is νa ()Va/na).
δP It follows from eqs 11 and 12 that
 (7)
δt
( ) ( )
z
δµa δ ln P
µa - T ) h* - RT2 (13)
where the transient variables of eqs 5 and 7 represent the gas- δT na δT na
phase pressure (P, atm), the temperature of gas and adsorbent
(T, K), the gas-phase mole fraction of component i (yi), the gas- Equation 10 can be differentiated with respect to na at constant
phase molar density (F, mol/cm3), the gas-phase molar heat P and T and with respect to T at constant na to obtain

( )
capacity (Cg, cal/mol/K), the molar gas flow rate through the
column based on empty cross section of adsorber (G, mol/cm2/ δGa
) µa (14)
s), the surface excess of component i (nmi , mol/g), and the total δna P,T

( ) ( )
amount of component i in the adsorber (nji, mol/cm3), as
δGa δP
functions of a distance z (cm) in the adsorber column at time t ) -Sa + Va (15)
(s). CA (cal/g K) is the heat capacity of the total adsorption δT na δT na

system at t and z.9  and Fb are, respectively, the helium void


Equation 14 can be differentiated with respect to T at constant
fraction of the adsorber (cm3/cm3) and the bulk density (g/cm3)
na, and eq 15 can be differentiated with respect to na at constant
of the adsorbent. The heat balance equation assumes instanta-
P and T and the two results equated to obtain
neous thermal equilibrium between the gas and the Gibbsian

( ) ( ) [( ) ] ( ) ( )
adsorbed phases. All of the above-described variables can be
δSa δµa δ δP δVa δP
experimentally measured unambiguously. - ) - Va a -
δna P,T δT na δn δT na P,T δna P,T δT na
Equations 5-7 can be simultaneously solved with the
(16)
appropriate multicomponent adsorption equilibria and kinetic
models (GSE framework) in conjunction with the appropriate We now consider a process where a differential amount (dn) of
initial and boundary conditions for the steps of the adsorption pure adsorbate is transferred from the gas phase to the adsorbed
process in order to estimate the separation performance of the phase while keeping the system closed (dn + dna ) 0) and
process.2 Thus, they show the practical usefulness of the isosteric maintaining P and T as constants. This can be achieved by fitting
heats of adsorption defined by eqs 2-4 using the GSE model. the gas phase of Figure 1b with a frictionless piston (as shown
by Figure 1c) and then (a) by differentially moving the piston
so as to decrease the total void volume of the system by dV0
Isosteric Heat of Adsorption by Conventional Model (cm3/g) in order to keep P constant and simultaneously (b) by
removing a differential quantity of heat (dQ, cal/g) from the
We now focus on the adsorption thermodynamics for the thermostated system at T. By applying the energy balance for
conventional model of Figure 1b. Only the adsorption from a a closed system with heat transfer and mechanical work at
pure ideal gas will be considered for simplicity. However, a constant P and T,12 one has
fairly detailed development is given because the published
literature on this subject is often not very rigorous.3,4 dU° ) -dQ - P dV0 constant P, T (17)
The key thermodynamic relationships for the adsorbed phase
Where U° ()U + Ua) is the total internal energy of the closed
described by Figure 1b (pure gas only) may be written as3,8
system of part b or c of Figure 1, U ()nu*) is the total internal
energy of the gas phase, n is the total moles of adsorbate in
dUa ) T dSa - P dVa + µa dna (8) that phase (n + na ) constant), and u* (h* ) u* + RT) is the
molar internal energy of the gas at T.
dHa ) T dSa + Va dP + µa dna (9) The total volume of the gas phase (V ) V0 - Va) of parts a
dG ) -S dT + V dP + µ dn
a a a a a
(10) and b of Figure 1 is given by

nRT RT
where Ua, Va, Sa, Ha ()Ua + PVa), Ga ()Ha - TSa) are, V) ; dV ) - dna constant P, T (18)
P P
respectively, the internal energy, the volume, the entropy, the
enthalpy, and the Gibbs free energy of the total adsorbed phase P dV0 ) P dVa - RT dna constant P, T (19)
containing na moles of a pure adsorbate per unit amount of the
adsorbent. The chemical potentials of the adsorbate in the Equations 8-19 can be combined to get
6542 J. Phys. Chem. B, Vol. 103, No. 31, 1999 Sirca et al.

[ ]
δQ
δna ( ) [ ( ){ ( )
) h* -
δHa
δna
) qj 1 -
Va na δqj
V qj δna P,T
+

( ) }]
P,T P,T

na δVa
+1 (20)
Va δna P,T

qj ) RT2 (δ δTln P) na
(21)

Equation 20, which was previously unpublished, provides the


rigorous relationship between the variable qj and the differential
heat to be removed from (added to) the system of Figure 1c
when a differential amount (dna) of pure adsorbate is ad(de)-
sorbed at constant P and T. However, if the molar density of
the actual adsorbed phase is much greater than that of the gas
phase (Fa . F; Va , V), then eq 20 simplifies to

( ) δQ
δna P,T
≈ qj (22)

provided that the terms inside the second bracket on the right-
hand side of eq 20 are relatively small. Figure 2. Sketch of the calorimeter sample cell (a) and the calorimeter
Most published literature on adsorption thermodynamics assembly (b).
derives eqs 21 and 22 by assuming that Va , V, and defines the
variable qj as the isoteric heat of adsorption for a pure ideal (V0, cc/g) and dosage (Vd, cc/g) sides are measured. The sample
gas3,4 because eq 21 shows that qj can be calculated from the side is then saturated with a multicomponent gas mixture at P0,
adsorption isosteres (plots of P against T at constant na). T0, and yi0 and the dosage side is filled with a pure gas i (a
Equation 20 shows that eq 22 is strictly valid only when Va component of the gas mixture of interest) at pressure Pd0 (>P0).
, V and the terms [(δ ln qj/δ ln na)P,T] and [(δ ln Va/δ ln na)P,T] A very small amount (∆Ni) of the pure gas i is then slowly
are small. The first criterion may be valid for adsorption of a introduced into the sample side from the dosage side and the
vapor well below its critical temperature, where the adsorbed valve is closed. The sample side is then allowed to reach a new
phase may be liquid like3. Otherwise, eq 22 may not be correct. equilibrium state. The temperature [T(t)] of the gas entering the
The term (δqj/δna)P,T is (a) equal to zero for an energetically sample side is continuously monitored. The total quantity of
homogeneous adsorbent and (b) relatively small for a weakly heat evolved (consumed) in the calorimeter cell (∆Qi) during
heterogeneous adsorbent.9 The term (δυa/δna)P,T is also expected the entire process is obtained by integration of the calibrated
to be small when the absorbed phase is liquid-like. Thus, the thermopile output (voltage vs time). The change in the partial
second criterion for validity of eq 22 may also be satisfied when pressure of component j of the gas mixture in the sample side
υa , υ and the adsorbent is homogeneous. In contrast, the (∆pji) is measured at the end of the process.
definition of q by the GSE model [eqs 2-4] does not require
any assumptions about the nature of the adsorbed phase, and it The amount of pure gas introduced into the sample side during
can be easily used for practical process design purposes. The the above-described process is
parallel between the forms of eq 4 for a pure gas (yi ) 1) and
eq 21 suggests that qi be called the isosteric heat of adsorption
of component i of a gas mixture. A more precise terminology
for qi is “isoexcess heat of adsorption of component i” for a
∆Ni ) ∫0t*Ṅi dt; Ṅi ) Vd[ ]dFd
dt
(23)

multicomponent gas mixture. For pure gas adsorption qj and q


where Ṅi is the rate of introduction of the pure gas i into the
are identical, if nm ) na, which is satisfied only if υa , υ.
sample side. It can be calculated by measuring the rate of change
of density (Fd) in the dosage side. The total time taken to
Calorimetric Measurement of Multicomponent Isosteric complete the process is t*.
Heat of Adsorption The enthalpy of pure gas i introduced (∆Hin) into the sample
side during the process is given by
A Tian-Calvet type heat flux microcalorimeter can be used
to directly estimate the multicomponent gas isosteric heats of
adsorption defined by the GSE model.9 Figure 2a is a sketch of ∫0t*Cgi/ [T(t) - T0]Ṅi dt
the calorimeter cell which is surrounded by thermopiles for ∆Hin ) (∆Ni)hhi; hhi ) (24)
directly measuring the heat flux through its walls. Figure 2b ∫0t*(Ṅi) dt
shows the schematic drawing of the calorimeter assembly. It
consists of the calorimeter cell, called the “sample side”,
connected to a gas holder, called the “dosage side”, through a where hhi is the time averaged molar enthalpy of pure gas i
valve. The gas-phase pressure and composition of the sample introduced into the sample side during the above-described
side and the gas-phase pressure of the dosage side can be process. hhi is equal to zero (assuming ideal gas) if the gas
continuously monitored. The entire system is thermostated at a entering the sample side is at the base temperature of the
constant temperature T0. A unit amount of regenerated adsorbent experiment [T(t) ) T0].
is placed in the sample side, and the helium voids of the sample The mass balances for the components of the gas mixture
Isosteric Heat of Adsorption: Theory and Experiment J. Phys. Chem. B, Vol. 103, No. 31, 1999 6543

(assuming ideal gas) for the differential process yield9

V0
∆Ni ) ∆nm
i + ∆pii (25)
RT0
V0
∆Nj*i ) 0 ) ∆nj*i
m
+ ∆pji (26)
RT0
An energy balance for the sample side of the calorimeter (open
system, ∆Hout ) 0, no shaft work) yields9,12
Figure 3. Test results of blank experiment: (a) plot of thermopile
∆Uoi ) ∆Hin - ∆Qi (27)
output signal (voltage vs time); (b) plot of gas temperature entering
calorimeter cell against experimental time.
where ∆Uoi is the total change in internal energy of the sample
side during the experiment. algorithm for data analysis outlined in the previous section. The
It can be shown by combining eqs 2-4 and 24-27 that for general design concepts of our calorimeter system were similar
an ideal gas9 to those used by Myers, Gorte, and their co-workers.13,14 It

{ }
consisted of two identical calorimeter cells (sample and refer-
∆Qi υ0∆pji qj ence) made from cylindrical stainless steel vessels. The sides
∆Ni
) qi - ∑j ∆N - 1 + hhi i ) 1, 2, ... N and the bottom of the calorimeter cells were covered with
i RT0 custom-made thermopiles manufactured by the International
(28)
Thermal Instrument Company of California. The tops of the
where qi is the isosteric heat of adsorption of component i calorimeter vessels were fitted with Zytel lids and thermal shunts
[defined by eqs 2-4] of an N component gas mixture (i ) 1,2, that minimize heat loss through the tops and redirect any heat
... N) at P0, T0, and y0i (or nm 0 m
i and T ). ni is the equilibrium
flow in that direction to the thermopiles. The sample and
surface excess of component i of the gas mixture at P0, T0, and reference cells were installed inside snugly fit holes cut into a
y0i . large aluminum block to maintain constant base temperature
A total of N experiments must be carried out around the base around the thermopiles. The sample cell was connected to a
saturation conditions of P0, T0, y0i (or T0 and nm gas supply chamber (dosage cell) through a metering valve.
i ) by separately
introducing differential quantities of each pure gas (∆Ni, i ) 1, Several multiport valves and interconnecting lines were used
2, ... N). This will generate N independent equations analogous to (a) evacuate the sample cell and flow the initial saturating
to eq 28 that relate N different unknowns (qi). Consequently, qi gas over the clean adsorbent at given values of P0, T0, and y0i ,
can be estimated for a given set of values of T0, P0, y0i (or T0 and (b) evacuate the dosage cell and filling it with the dosing
and nm gas at Pd0 and T0. The sample side was instrumented with
i ).
For adsorption of a pure ideal gas (component i), eq 28 differential pressure cells and thermocouples for continuous
monitoring and recording of pressure and temperature in these
simplifies to (base conditions of T0, P0, y0i ) 1)
cells. A residual gas analyzer (mass spectrometer) was connected

[( ) ( )]
∆Qi ∆Pi to the sample cell through a leak valve for continuously
- hhi - V0 monitoring the gas composition in the cell. A thermocouple
∆Ni ∆Ni

[ ( )]
q0i ) (29) monitored the temperature of the gas entering the sample cell
V0 ∆Pi from the dosage cell during the experiment. The entire
1- calorimetric assembly was kept inside a constant-temperature
RT ∆Ni
air bath. Figure 2 shows a schematic diagram of the sample
where ∆Pi is the change in the gas-phase pressure in the sample cell. The total amount of adsorbent in the cell was typically
side during the process, and qi0 is the isosteric heat of 8-12 g.
adsorption of pure gas i at P0 and T0 (or T0 and nm0 m0 There were two output signals (voltage against time) from
i ). ni is the
equilibrium surface excess of pure gas i at P0 and T0. the calorimeter assembly during the experiments. They were
We now consider the special case of the above-described produced by (a) the sample cell and (b) the reference cell. The
experiment using a pure ideal gas where (a) the gas is difference between these two outputs was used to estimate the
nonadsorbing or (b) the adsorbent is absent, and where hhi is actual heat liberated (consumed) during the ad(de)sorption
equal to zero. The heat evolved in the sample side of the experiment. The signal from the reference cell was used to
calorimeter (∆Q*) for introduction of (∆N*) moles of pure gas, correct for any spurious heat generated inside the calorimetric
in this case (qi ) 0), is given by cell due to temperature fluctuations in the aluminum block.
Figure 3a shows a typical output signal from the calorimeter.
∆Q* ) V0∆P* (30) The voltage-time output signal was transformed into the rate
of heat production vs time data by electrically generating a
where ∆P* is the change in the gas pressure of the sample side known quantity of heat inside the calorimeter and measuring
during the process. V0 is the helium void volume of the sample the output signal. A PC-based data acquisition/control system
side [(a) with adsorbent and (b) without adsorbent]. was set up to control switch valves and to record all experi-
mental data such as pressures, temperatures, compositions, and
Experimental Measurement of Isosteric Heat by heat fluxes as functions of time during the experiments.
Calorimetry
Examples of Calorimetric Data
We constructed a multicomponent differential calorimeter
(MDC) which utilizes the experimental protocol and the Blank Experiments. We carried out several blank experi-
6544 J. Phys. Chem. B, Vol. 103, No. 31, 1999 Sirca et al.

Figure 4. Plot of the quantity of heat liberated (∆Q*) during the blank
experiments (without adsorbents) against pressure change in the
calorimeter cell (∆P*).

ments using pure N2 and CO2 as adsorbates. These pure gases


were expanded from the dosage side to the calorimeter cell
containing no adsorbent (helium void, V0 ) 24.75 cm3). Several
different initial dosage side pressures (Pd0) were used with (a)
an initially evacuated calorimeter cell or (b) a calorimeter cell
containing pure gas at some initial pressure. The total heat
liberated during each of these tests (∆Q*) was measured as a
function of the corresponding change in gas pressure in the
calorimeter cell (∆P*).
Figure 3a shows a typical thermopile output signal from these
runs. The base temperature was 303.7 K. The connecting valve
between the dosage and calorimeter cells was opened at t )
2.5 min, when the voltage output signal rose very sharply to its
Figure 5. Pure gas adsorption isotherms of (a) N2 and (b) CO2 on the
maximum value and then it slowly decayed down to the original
pelletized silicalite sample at 303.5 K measured using the calorimeter
baseline value in about 14 min ()t*) after the valve was opened. assembly as a volumetric adsorption apparatus.
Figure 3b shows that the temperature of the gas entering the
calorimeter cell during this period remains practically constant
excess isotherms (nm0 0 0
i as functions of P at constant T ) on the
[T(t) ) T0]. Thus, the term hhi in eq 28 is zero. Consequently,
adsorbent using eq 25 if the sample and dosage sides are allowed
according to eq 29, a plot of ∆Q* against ∆P* should be a
to reach equilibrium during the process:
straight line through the origin with a slope equal to V0,
irrespective of the nature of the gas used.
Figure 4 shows such a plot for both CO2 and N2. The slope V0∆Pi
∆Ni ) ∆nm0
i + (31)
of the line is 23.54 cm3, which is within 5% of the independently RT
measured helium void of the calorimeter cell. This result
validates eqs 28 and 30 for the special case of blank experiments. A cumulative set of differential expansion experiments can be
Experiments with Adsorbents. We measured the isosteric carried out to generate the pure gas surface excess isotherm
heats of adsorption of pure N2 and CO2 on a pelletized sample using eq 31 by starting with a clean adsorbent. The procedure
of silicalite (obtained from UOP Corporation) using the above- was identical to that for a conventional volumetric adsorption
described calorimeter and using eq 28 for data analysis. q0i was apparatus.15
measured as functions of P0 at 303.5 K. Figure 5 shows the pure N2 and CO2 isotherms at 303.5 K
The silicalite pellets (1/8" diameter, 1/4" long) were regener- on the silicalite sample obtained by using eq 30. These isotherm
ated by heating under vacuum (1 µm) at 300 °C and then data can be combined with the isosteric heat data for the pure
transferred to the calorimeter cell under dry N2 in a glovebox. gases measured at different values of P0 for obtaining qi0 as
They were then subjected to a vacuum (1 µm) for 1 h at the functions of nm0 0
i at a constant value of T . Figure 6 shows such
temperature of the experiment before the calorimetric tests were results (open circles) for pure N2 and CO2 adsorption on the
started. pelletized silicalite sample. The figure also shows the pure gas
The thermopile output signals for all of these runs were very isosteric heats of adsorption of CO2 and N2 on the same silicalite
similar in shape to that shown by Figure 3a. The temperatures sample (closed circles) calculated independently from surface
of the gas entering the calorimeter cell during these runs were excess isotherms at two different temperatures (not shown)
also very close to the base temperature, like that shown by measured by a conventional volumetric adsorption apparatus.15
Figure 3b. Thus, the term hhi in eq 29 was equal to zero for all The pure gas form (yi ) 1) of eq 4 was used to calculate the
of these runs. The differential quantities ∆Qi, ∆Ni, and ∆Pi of isosteric heats from surface excess isotherms at two tempera-
eq 29 were measured for all runs and q0i was calculated as a tures. It may be seen from Figure 6 that the pure gas isosteric
function of P0 at constant T0. heats and their variation with surface excess obtained by these
It should be noted here that the above-described experiments two methods matched very well in the range of the data. This
with pure gas can also be used to calculate pure gas surface demonstrates the validity of eq 29. The calorimetric data of
Isosteric Heat of Adsorption: Theory and Experiment J. Phys. Chem. B, Vol. 103, No. 31, 1999 6545

occupied by CO2 on the pelletized sample at higher pressures


are predominantly the silicalite sites because the isosteric heat
of adsorption of CO2 on the pellet in that region matches that
of pure crystals very well. A key question then is “what is the
source of high-energy sites for adsorption of CO2 at low
pressures in the pelletized silicalite sample?”
A chemical analysis of the pelletized silicalite sample showed
that it contained ∼19.0% alumina as a binder. The previously
reported isosteric heat of adsorption of pure CO2 on γ-alumina
at the limit of zero coverage is about 14 kcal/mol.16 The isosteric
heat then drops drastically as the CO2 coverage increases. We
suspect that the presence of alumina binder in the silicalite pellet
is the source of its energetic heterogeneity for CO2 adsorption.
The strong interaction between the large quadrupole moment
of CO2 and the highly polar alumina binder appears to be the
reason for high isosteric heat of adsorption of CO2 on the
pelletized silicalite sample at low pressures. The interaction
between the weak quadrupole moment of N2 and the alumina
binder does not introduce significant heterogeneity for N2
adsorption on the silicalite pellet.

Summary

The isosteric heats of adsorption of the components of a gas


mixture are critical variables for the design of practical gas
separation processes. They can be defined unambiguously using
the Gibbsian Surface Excess (GSE) model of multicomponent
gas adsorption without making any extraordinary assumptions
about the nature and size of the adsorbed phase as required by
the conventional thermodynamic models of adsorption using
Figure 6. Isosteric heats of adsorption of (a) pure N2 and (b) pure actual amounts adsorbed as the primary variables. The isosteric
CO2 on the pelletized silicalite sample found by calorimetry (open or isoexcess heats of adsorption defined by the GSE framework
circles) and by volumetric adsorption apparatus (closed circles). can be experimentally measured by using multicomponent
differential calorimeters (MDC) and they can be directly used
Figure 6 for both gases were measured on the silicalite sample to describe heat balance in batch or flow adsorbers.
several times by cleaning the adsorbent by evacuation. The data A Tian-Calvet type MDC is described for direct measure-
were extremely reproducible. ment of multicomponent isosteric heats of adsorption in
The silicalite is a nonpolar homogeneous adsorbent with conjunction with the algorithm for calorimeter data analysis.
practically no cation exchange capacity. Consequently, the Isosteric heats of adsorption of pure N2 and CO2 were measured
isosteric heats of adsorption of N2 (with weak quadrupole as functions of adsorbate loading on a pelletized sample of
moment of 1.5 × 10-26 esu cm2) and CO2 (with large silicalite using the MDC. The isosteric heat of adsorption of
quadrupole moment of 4.3 × 10-26 esu cm2) on the silicalite N2 on the silicalite sample was found to be independent of its
are expected to be independent of their loadings. Previous adsorbate loading, indicating that the adsorbent was energetically
calorimetric measurements of isosteric heats of adsorption of homogeneous toward N2 adsorption. The isosteric heat of
N2 and CO2 on pure unbound silicalite crystals exhibited that adsorption of CO2 on the same silicalite sample, on the other
behavior.13 The isosteric heats of adsorption of N2 and CO2 on hand, decreased with increasing adsorbate loading, indicating
the silicalite crystals were, respectively, 4.20 kcal/mol at 296.0 energetically heterogeneous behavior. The presence of polar
K and 6.59 kcal/mol at 303.7 K and they were constants alumina binder in the silicalite sample, which has a very large
(independent of nm0 i ).
isosteric heat of adsorption for CO2 at low coverages, was
The data of Figure 6 shows that the isosteric heat of suspected to be the cause of heterogeneity for CO2 adsorption.
adsorption of N2 on the silicalite pellet is indeed constant (∼4.13
kcal/mol) over the range of the data (0 e nm0 e 0.6 mol/kg). References and Notes
i
This agrees extremely well with the previously published (1) Sircar, S. Pressure Swing AdsorptionsResearch Needs in Industry.
isosteric heat values for N2 on silicalite.13 On the other hand, In Fundamentals of Adsorption, Proceedings of Engineering Foundation
Conference held at Sonthofen, Germany; Mersmann, A. B., et al., Eds.;
the data of Figure 6 shows that the isosteric heat of adsorption Engineering Foundation: New York, 1991; p 815.
of CO2 on the silicalite pellet is very high (∼9.5 kcal/mol) at (2) Hartzog, D. G.; Sircar, S. Adsorption 1995, 1, 133.
the limit of zero coverage and then it gradually decreases and (3) Young, D. M.; Crowell, A. D. Physical Adsorption of Gases;
levels off at a value of ∼6.3 kcal/mol. Thus, the pelletized Butterworths: Washington, DC, 1962.
silicalite sample exhibits significant energetic heterogeneity for (4) Hill, T. L. J. Chem. Phys. 1949, 17, 520.
CO2 adsorption. In other words, the pelletized silicalite sample (5) Everett, D. H. Colloq. Int. CNRS 1971, 201, 45.
(6) Cardona-Martinez, N.; Dumesic, J. A. AdV. Catal. 1992, 38, 149.
possesses some high-energy sites for CO2 sorption which are
(7) Gibbs, J. W. The Collected Works of J. W. Gibbs; Longmans and
preferentially occupied by CO2 at low pressures. At higher Green: New York, 1928.
pressures, the lower energy sites (∼6.3 kcal/mol) of the sample (8) Sircar, S. J. Chem. Soc., Faraday Trans. 1 1985, 81, 1527.
are predominantly occupied by CO2. It appears that the sites (9) Sircar, S.; Rao, M. B. Heat of Adsorption of Pure Gas and
6546 J. Phys. Chem. B, Vol. 103, No. 31, 1999 Sirca et al.

Multicomponent Gas Mixtures in Microporous Adsorbents. In Surfaces of Engineering Thermodynamics; Prentice Hall: Englewood Cliffs, NJ, 1972;
Nanoparticles in Porous Materials; Schwarz, J. A., Contescu, C., Eds.; pp 98-101.
Marcel and Dekker: New York, 1999; Chapter 19, pp 501-528. (13) Dunne, J. A.; Mariwala, R.; Rao, M. B.; Sircar, S.; Gorte, R. J.;
(10) Sircar, S. J. Chem. Soc., Faraday Trans. 1 1985, 81, 1541. Myers, A. L. Langmuir 1996, 12, 5888.
(11) Prausnitz, J. M. Molecular Thermodynamics of Fluid Phase (14) Parrillo, D. J.; Gorte, R. J. Catal. Lett. 1992, 16, 17.
Equilibria; Prentice Hall: Englewood Cliffs, NJ, 1969. (15) Golden, T. C.; Sircar, S. J. Colloid Interface Sci. 1991, 147, 274.
(12) Balzhiser, R. E.; Samuels, M. R.; Eliassen, J. D. Chemical (16) Rosynek, M. P. J. Phys. Chem. 1975, 79, 1280.

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